New cyclotrisiloxanes



2,979,519- NEW CYCLOTRISILOXANES.

States. Patent; 7

Ogden R. Pierce andiGeorge W. Holbrook, Midland,

Mich., 'assignors to Dow Corning Corporation, Midland, Mich., a corporation of Michigan NoDrawing. Filed June. 21, .1956, so. No. 594,108.;

*Cl'airns. or. 26094481) This invention relates to. 'cyclotrisiloxanes containing fluorine groups in the side chain.

' The organopolysiloxane rubbers which have met with the greatest commercial successhave been those "which contain phenyl and methyl groups attached to the silicon atoms. The utility and versatility of these materials has been well established andthey have found wide application in a multitude of industries. Howeven theserubbers novel compositions of matter'which are particularly-'useful as intermediates in the preparation of organopolysiloxane rubbers.

This invention relates tocyclotrisiloxanes of the unit formula M. nornomsro where R is a perfluoroalkyl radical of from 1 to inclusive carbon atoms.

For the purpose of this invention R can be any perfluoroalkyl radical of from 1 to 10 inclusive carbon atoms.

such as CF C F C F and C F These perfluoroalkyl groups can be either straight or branch chained radicals.

The compositions of this invention may be prepared starting with the chlorosilanes of the formula Me RCHzCH2SiC12 These in turn may be prepared by the reaction of an alkylene of the formula RCH-CH with methyldichlorosilane in the presence of a peroxide or platinum catalyst at temperatures of from 150 to 300 C.

The chlorosilanes can be hydrolyzed in the conventional manner and the resulting hydrolyzate is then heated with an alkali metal hydroxide or an alkali metal salt of 'a siloxane under conditions which cause the cyclotrisiloxane to distill from the, reaction mixture; If desired, this crack ing can be carried out under a fractionating column whichv will return the higher boiling cyclics to the reaction zone. In this way the siloxane can be converted quantitatively to the cyclic trimer.

An alternative method which may be employed in those cases where the cyclic trirner is a crystalline material involves heating the crude hydrolyzate with the aforesaid alkaline catalysts under conditions where the volatile cyclic materials are removed by distillation. The cyclic trirner may then be crystallized from the distillate by cooling and the crystals removed by filtration. By repeating this process it is possible to' obtain a high yield of the crystalline trimer.

In general the cracking operations for the preparation o r 2,979,519 Patented'Apr-J1Q of the trimer range from 200 to 400 C. and may be carried out at reduced pressure or at atmospheric pressure. When the higher temperatures are employed, it is preferable that the operation be carried out'in anitrogenatmosphere. 7 i

It has been found that commercially successful rubbers cannot be prepared, by known methods, from the crude hydrolysis products of chlorosilanes of the formula Me RGHzGHzSiChI. or from cyclosiloxanes of the formula RCmCHtSiO). where x is 4 or more. Consequently the cyclic trisiloxane's of this inventionrepresent the only materials'i'n this class of silicon compounds which can be polymerized to rubber grade polymers. The method of polymerizing the siloxarres of this invention. to high polymers isfully described in the copending application of Oscar K. Iohannson, Serial No. 594,107, filed simultaneously herewith and 'now abandoned. The excellenceof the rubbers prepared fromthe compositions of this invention is'shown in the copending application ofv Eric D. Brown, Serial No. 594,113, also fil'ed simultaneously herewith. Both'of s aid 'copending applications are hereby made a part of this specification by reference.

The following examples are illustrative only and should not be'construed as limiting the invention which'is properly'delineatedirr the appended claimsr.

- Example 1 1120 g. of

was hydrolyzed with an excess of water at 0 C. The I hydrolyzate was dissolved in ether, washed neutral and dried and the solvent was removed by evaporation.

4.4 g. of potassium hydroxide was added to thehydrolyzate and the mixture was heated under a fractionating column at a pressure of 8 mm. at a temperature of to 200 C. 750 g. of the cyclotrisiloxane of the unit formula I Me 0 FaCHzCHzSiO I was obtained. This material had a boiling point of 115 C.

at.8 mm. pressure. When cooled it was a white, crystalline material. The supercooled liquid had a refractive index at 25 C. of 1.3654.

Example 2 g. of

C F OHZCHrSiCIr Me (CzFrCHrCHzSiO):

which boiled at 129 C. at 11 mm. pressure and had a refractive index at 25 C. of 1.3501.

. Example 3 The compound was hydrolyzed as in Example 2. The resulting hydrolyzate was heated with lithium hydroxide at a temperature of 20 0 to 230C. at reduced pressure. The distillate ob-. tained was then reheated with additional lithium hydroxide at 400 C. at atmospheric pressure in an atmosphere of nitrogen. The distillate was cooled to 0 C. whereupon a crystalline fraction was formed. This was removed by filtration and was shown to have the formula .T'hiscompound melted at 59 to 60 C. and had a boiling point of 128 C. at .4 mm.

That which is claimed is: 1. A cyclic trisiloxane of the unit formula Me I RCHzCHtSlO where Me represents a methyl radical and R is a pe rfluoroalkyl radical of from 1 to 10 inclusive carbon atoms.

2. A cyclic trisiloxane of the unit formula Me cFaomcmsio where Me represents a methyl radical.

3. A cyclic trisiloxane of the unit formula Me C2F5CH2CH2SiO where Me represents a methyl radical.

4. Acomposition of matter consisting essentially of a cyclic t'risiloxane having the formula [CF CH CH (CH SiO] 3 5. Av method for producing cyclic trisiloxanes of the I formula [RCHaOHzQEJa in which Me represents a methyl radical and each R is a perfluoroalkyl radical of no more than 10 carbon atoms, said method consisting essentially of heating a mixture consisting essentially of higher polymers of the unit formula Me BOHgCH StO with a catalyst selected from the group consisting of alkali metal hydroxides and alkali metal salts of siloxanes under conditions of temperature and pressure at which the aforesaid cyclic trisiloxane will distill from the reaction mixture and at which higher boiling cyclics will return to the reaction mixture.

References Cited in the file of this patent UNITED STATES PATENTS 2,455,999 Hyde Dec. 14, 1948 2,651,651 Simons et a1 Sept. 8, 1953 2,686,194 Passino et a1 Aug. 10, 1954 2,715,113 Gordon Aug. 9, 1955 2,860,152 Fletcher Nov. 11, 1958 OTHER REFERENCES Rochow: An Introduction to the Chemistry of the Silicones, 2nd edition. John Wiley and Sons,jInc., New York (1951), pages 7980. I

Pierce et al.: Journal American Chemical Society, vol- 5 111116 75 (November 1953 pages 5618-5620. 

1. A CYCLIC TRISOLOXANE OF THE UNIT FORMULA 